Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression

Definitions

• the specific moieties symbolically represented in the above formula are defined in the specification.
• the active antifoggant illustrated above may be incorporated into a silver halide emulsion layer, a protective layer and in intermediate layer or the like.
• the present invention relates to an improved photographic silver halide light-sensitive element containing an antifoggant.
• a photographic light-sensitive element in which the formation of fog may effectively be prevented without a reduction in sensitivity may be obtained by the incorporation in a silver halide layer, a protective layer and an intermediate layer or the like, of a compound which contains a repeating unit represented by the following formula:
• R represents a member selected from the group consisting of OR
• the compound shown above When the compound shown above is present in the silver halide emulsion layer, it is preferred that it be present in amounts from about 0.0] g. to about 50 g./ l mole of silver halide in the emulsion. When the compound shown above is added to a protective layer, it is preferred that the compound be present in amounts from about 0.05 g. to about 250/ 1 kg. of I gelatin in the layer. When the compound shown above is added to an intermediate layer, it is preferred that the compound be present in amounts from about 0.05 g. to about 250 'g./ l kg. of gelatin in the layer.
• An object of this invention is to provide a photographic light-sensitive element in which the formation of fog is effectively prevented without a reduction in sensitivity.
• Another object of this invention is to provide a photographic light-sensitive element which can be stored for a long :period of time without the formation of fog and which will remain stable during storage.
• Still another object of this invention is to provide a photographic emulsion having a good preservability, that is, one which will illustrate less degradation in sensitivity and contrast ,when preserved for a long period of time.
• a still further object of this invention is to provide a photographic light-sensitive element in which the formation of fog, caused when the photographic silver halide emulsion layer is processed in a formalin-containing bath before developing in order to preliminarily harden the gelatin film, is prevented without lowering the sensitivity of the light-sensitive photographic element.
• R and R each represents a member selected from the group consisting of (i) a hydrogen atom: (ii) an alkyl group having one to l2 carbon atoms, a hydroxyalkyl group, a sulfoalkyl group, a salt thereof, a carboxyalkyl group, a salt thereof, and an aralkyl group, each of said groups having from one to four carbon atoms in the main straight carbon chain thereof; (iii) an unsubstituted aryl group having from six to 12 carbon atoms, an aryl group having from six to 12 carbon atoms substituted by a member selected from the group consisting of a sulfo group, a salt thereof, a sulfoxy group, a salt thereof, a hydroxyl group, an alkyl group having from one to four carbon atoms, an alkoxy group having from one to four carbon atoms, and a halogen atom; an un
• an alkyl group having from one to four carbon atoms and a hydroxyalkyl group having from one to four carbon atoms an arylene group having from six to 12 carbon atoms, an arylene group having from six to 12 carbon atoms substituted by a member selected from the group consisting of a sulfo group, a salt thereof, a carboxyl group, a salt thereof, an alkyl group having from one to four carbon atoms, an alkoxy group having from one to four carbon atoms and a halogen atom, a cycloalkylene group having from six to 12 carbon atoms, and a cycloalkylene group having from six to 12 carbon atoms substituted by a member selected from the group consisting of a sulfo group, a salt thereof, a carboxyl group, a salt thereof, an alkyl group having from one to four carbon atoms, an alkoxy group having from one to four carbon atoms and a halogen atom,
• the antifoggant used in the present invention is a high molecular compound having s-triazine rings prepared by the method described below.
• the main component of the antifoggant is considered to be composed of a polymer having more than four s-triazine rings in the main chain.
• the aforesaid antifoggant having a repeating unit represented by general formula (I) described above may be prepared by the polycondensation reaction of a s-triazine compound repr esented bygeneral formula H [wherein X represents a halogen atom such as a chlorine atom or a bromine atom, R, has the same meaning described in connection with general formula (l)]and a diamino compound, represented by general formula (III) or (IV) [wherein R R;,, R,, R Y,, Y Y Y,, Z, k, and m have the same meaning as described in connection with general formula (1)] or by the polycondensation reaction of a bis-( halogenos-triazine) compound represented by general formula (V) or [wherein X has the same meaning described in connection with general formula (II) and R,, R R R, R Y Y2, 3, 4, Z, k and m have the same meaning as described in connection
• halogeno-s-triazine compounds represented by general formulas (II), (V) and (VI) described above may be prepared from cyanuric chloride by the method described in the Journal of the American Chemical Society”; Vol. 73, 2981-2992 195 l The antifoggants used in this plained in greater detail.
• R aforesaid formulas (ll), (V) and (VI), may be as follows:
• the preparation of the antifoggant having a repeating unit represented by general formula (I) described above may be prepared by the following two illustrative general methods.
• an alkali carbonate e.g., pyridine, 2,4,6-trimethylpyridine, and diamino- HN-OH OHz-(JCH;OHzNH-, HN-(OH,) -N i y n n b.
• the antifoggant of the present invention may, of course, be CHFCH prepared by methods other than those described above.
• Typical examples of a compound having a repeating unit HN-C represented by general formula (I) or (II) are illustrated 0H3 GHQ-CH2 CH3 below:
• the number of s-triazine rings The number of S-triazine rings Com ound 1 N p LK TNH(CH2MNHJ T wm .1
• the 2,4-dichl0ro-6-(-2-hydroxyethylamino)-s-triazine (209 g.) obtained was mixed with 2 liters of water and while stirring the mixture at a temperature of 2025 C., a solution consisting of 70 g. of 1,3-diaminopropane and 300 ml. of water was added to the mixture over a one hour period. Thereafter, the temperature of the system was elevated to 3035 C. and a solution consisting of 168 g. of sodium carbonate and 1 liter of water was added to the mixture over a 40-minute period. After the addition thereof, the temperature of the system was elevated gradually and stirred for 3 hours at 100 C.
• the reaction mixture was filtered after being allowed to cool, and the product thus recovered was washed with water, until the washings became neutral, and dried to provide 200 g. of the white powders of compound 1.
• the intrinsic viscosity of compound measured in dimethylformamide at 35 C. was 0.104.
• the product f 2 '4 'Dihydr1,yjsulfiethylaminmg was recrystallized from a dioxane-water 1:] mixed solution to triazine 0 5.0 provide 184 g. of the white crystal of l,3-bis(2'-chloro-4'- 5 i hydroxyethylamine-s-triazine-6-ylamino)-propane, having a I gg 'z gjg gf' 0 melting point (decomposed) of 276 C. hydroxyethylamino) A mixture of 42.5 g.
• the physii f i fi words g g f n ofbthe cal retardance of the antifoggant of this invention compared' "i F con ame m compoun S wl now e exwith that of known antifoggant is shown in the table below.
• the physical retardance value was observed by con- 3" may be Prepared by the methods dcscvbed ventional physical retardance measuring methods for testing products prpzired by the polycondensaf'on, macho the chemical properties of photographic gelatin e.g., Testing of a compound and 3 3 for Photographic Gelatin (PAGI method); Commission pound are obtained as a mixture of polymers having different Testing Method for Photographic Gelatin (Japamn 1243 distributions of polymerization degree, depending upon reac- (1964) Specifically the measurement was pcrformed as in non conditions, such as reaction time, reaction temperature, the PA'GI method w'ith the exception that each of the reaction solvent, the catalyst, if one is used, and the mole ratio pounds was added to men gelatin and employed as the 40 of the dlhalogeno-s-tnazme compound to the dtammo comple.
• PAGI method Testing of a compound and 3 3 for Photographic Gelatin
• Commission pound are obtained as
• the 11 Compound I 9 antifogging effect and the physical inhibitance were then meal g 2 2'3 sured and the results are shown in the following table.
• the compound, having the repeating unit shown by general formula (I), used in this invention shows an excellent antifogging effect or stabilizing power for photographic silver halide light-sensitive elements, and does not harmfully influence any other useful photographic properties.
• the compounds of the invention may be used alone (or as mixtures thereof) as antifoggants or stabilizers. In addition, they may be used in combination with conventional antifoggants.
• the antifoggants of this invention may be added to the silver halide emulsion at stages before the emulsion is applied to a support, but is preferably added between after-ripening and coating. Further, it has been found that the antifoggant of this invention can be very effectively incorporated in a photographic layer other than the silver halide emulsion layer, such as, a protective layer other than the silver halide emulsion layer, such as, a protective layer adjacent the silver halide emulsion layer or an intermediate layer between silver halide emulsion layers.
• solvents such as water, dimethylforrnamide, dimethyl sulfoxide, water containing an acid (inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, etc. or organic acids such as acetic acid) or water containing an alkali (such as acid alkali carbonate, an alkali carbonate, or an alkali hydroxide), it is often desirable to add the antifoggant compound in the form of a solution in the aforesaid solvents.
• solvents such as water, dimethylforrnamide, dimethyl sulfoxide, water containing an acid (inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, etc. or organic acids such as acetic acid) or water containing an alkali (such as acid alkali carbonate, an alkali carbonate, or an alkali hydroxide).
• concentration of the antifoggant of this invention which may be used, but a suitable concentration is generally 0.01-50 g. per 1 mole of silver haand 0.05-250 g. per 1 kg. of gelatin when adding it to a protective layer or to an intermediate layer. 7
• the present invention is applicable to black and white negative emulsions, X-ray emulsions, the so-called coupler-inemulsion-type color photographic silver halide emulsions,
• a silver halide emulsion containing the antifoggant of this invention may be chemically sensitized by conventional methods, such as by the addition of a compound containing a labile sulfur, e.g., ammonium thiosulfate and allylthio urea (of, if necessary, The Theory of the Photographic Process"; 3rd edition, 1 13-1 16 (1966); McMillan Company, New York); a complex salt of monovalent gold and thiocyanic acid (ibid., page l 16) reducing sensitizers, such as amines, hydrazines or a heavy metal salt such as stannous chloride (ibid.; pages ll31l6); and polyalkylene oxide derivatives, or combinations thereof.
• a labile sulfur e.g., ammonium thiosulfate and allylthio urea
• a complex salt of monovalent gold and thiocyanic acid ibid., page l 16
• the emulsion used in this invention may further contain an inorganic hardening agent (ibid., page 55); or an organic hardening agent (ibid., pages 55-60).
• the silver halide emulsion in this invention may contain a wetting agent, for example, a nonionic surface active agent, such as polyoxyethylenenonylphenyl ether; an anionion ,surface active agent such as sodium alkylbenzene sulfonate or ;sodium N-alkanoxyl-N-alkyl taurate; an amphoteric surface iactive agent; or anionic surface active agent containing an ethylene oxide chain as described in Belgian Pat. No. 650,004.
• a wetting agent for example, a nonionic surface active agent, such as polyoxyethylenenonylphenyl ether; an anionion ,surface active agent such as sodium alkylbenzene sulfonate or ;sodium N-alkanoxyl-N-alkyl taurate
• the antifoggant used in this invention having the repeating unit represented by general formula (1) has properties which differ from those of conventional antifoggants in that the antifoggant of this invention has a high molecular weight, and the antifoggant of this invention shows excellent antifogging :efiects with respect to silver halide emulsions.
• lide when incorporating it in a silver halide emulsion layer 2,476,536 and 2,948,612 have been known, but they were sitivity of the emulsion has 3 After aging of 2 days at 50 C. at 80% relative humidity.
• the antifoggant of this invention can efi'ectively EXAMPLE 1
• Each ofthe antifoggants (l)(5), (l3) (l6) and (17) was incorporated in a sulfurand gold-sensitized, high-speed gelatin-silver iodobromide negative emulsion, respectively, and the resulting silver halide emulsions were applied to a film base and dried.
• the light-sensitive films thus prepared were exposed on an NSG Il-type sensitometer (made by Tokyo Shibaura Electric Co.) and developed in a developer having the following composition for 8 minutes at 20 C:
• the initial formation of fog was prevented by the antifoggants of this invention, and when the photographic film was developed after being aged for 2 days at C. and at a relative humidity of 80 percent, the formation of fog was also prevented, without a reduction in sensitivity.
• Potassium bromide Water to make 1 liter.
• EXAMPLE 3 Sodium Pyrophosphate 20 g. Sodium sulfate 50 g. 37% Formaldehyde [7 ml. l0% sodium hydroxide l ml. Water to make 1 liter.
• the light-sensitive films thus processed were washed with water for 4 minutes at 27 C.
• the films were then developed for 7 minutes at 27 C. in a developer having the following composition:
• Each of the antifoggants (l l), (12), (i5) and (20) of this invention were incorporated in an aqueous 5 percent gelatin solution, respectively.
• a sulfurand gold-sensitized gelatino silver iodo-bromide emulsion for use as a reversal color photographic material was coated on a glass plate of about 200 sq. cm., and dried. Then, 5 ml. of the gelatin solution prepared, as above was coated on the silver halide emulsion layer and dried.
• the thus double-coated photographic plates were exposed on an NSG ll-type sensitometer and developed for 7 minutes at 27 C. in a developer having the same composition as in example 3.
• composition of the hardening bath and the negative developer were the same as those in example 3.
• EXAMPLE 6 The antifoggant 14) of this invention was added to samples of a sulfur and gold-sensitized gelatino-silver iodo-bromide emulsion for use as a negative color photographic material.
• 1- hydroxy-4-sulfo-2-n-octadecyl naphthamide was incorporated therein as a coupler by adding 20 parts by weight of an aqueous alkaline solution of the coupler l g. of the coupler per 1.4 mol of a 1N sodium hydroxide) to 100 parts by weight of the emulsion.
• the photosensitive color film thus obtained was exposed and developed using standard techniques in a color developer having the following composition:
• the photographic film thus developed was further processed in a silver bleaching bath having the composition set out below and in a fixing bath having the composition set out below in order to remove the undeveloped silver halide and reduced silver:
• Bleaching solution Potassium l'erricyanide 100 g. Potassium bromide 20 g. Water to make I liter. Fixing solution Sodium thiosuifate 200 g. Sodium sulfite (anhydrous) 20 g. 28% acetic acid 45 g. Boric acid 7.5 g. Potassium alum 20 g. Water to make I liter.
• EXAMPLE 7 A dispersion of a coupler, l-phenyl-3[3'(N-propyl-N-octylamidoJ-propioamidel-s-pyrazolone, was prepared by distion of sodium dodecylbenzene sulfonate and stirred at 80-90" C. l Parts by weight of the dispersion thus prepared was added to 100 parts of a sulfurand gold-sensitized gelatinosilver iodo-bromide emulsion.
• EXAMPLE 8 To 100 parts by weight of a sulfurand gold-sensitized gelatino-silver chloro-bromide emulsion there was added 40 parts by weight of a percent aqueous alkaline solution of 3,5- dicarboxy- [(4-stearoyla.mido)benzoyl] acetanilide. Antifoggant (i) of this sion. After adjusting the pH to 8.0, the resulting emulsion was coated on a film base to a thickness of 6 microns.
• the densities thereof were measured by using a blue filter, a green filter and red filter respectively.
• the fog formation was remarkably reduced without substantially reducing the sensitivity.
• A represents a member selected from the group consisting of a polymethylene group having from 4-5 carbon atoms, and a polymethylene group having a heteroatomic group and forming a -6 membered ring together with a nitrogen atom;
• R R R and R each represent a member selected from the group consisting of
• an arylene group having 6-12 carbon atoms an arylene group having from 6-12 carbon atoms substituted by a member selected from the group consisting of a sulfo group, a salt thereof, a carboxyl group, a salt thereof, an alkyl group having from l-4 carbon atoms, an alkoxy group having from l-4 carbon atoms and a halogen atom, a cycloalkylene group having from 6-12 carbon atoms substituted by a member selected from the group consisting of a sulfo group, a salt thereof, a carboxyl group, a salt thereof, an alkyl group having from l-4 carbon atoms, an alkoxy group having l-4 carbon atoms and a halogen atom;
• Z represents a member selected from the group consisting of an oxygen atom, a sulfonyl group and a hydrocarbon residual group having from l-2 carbon atoms; and k and m each represents 0 or 1.
• a photographic silver halide light-sensitive element comprising a support having thereon a light-sensitive silver halide emulsion layer and a gelatin layer adjacent thereto, said gelatin layer containing a compound having a repeating unit represented by the following formula:
• a hydrogen atom selected from the group consisting of (i) a hydrogen atom; (ii) an alkyl group having from l--] 2 carbon atoms, a hydroxyalkyl group, a sulfoalkyl group, a salt thereof, a carboxyalkyl group, a salt thereof, and an aralkyl group, each of said groups having from l4 carbon atoms in the main straight carbon chain thereof; (iii) an unsubstituted aryl group having from 6-12 carbon atoms, an aryl group having from 6-12 carbon atoms substituted by a member selected from the group consisting of a sulfo group, a salt thereof, a sulfoxyl group, a salt thereof, a hydroxyl group, an alkyl group having from l4 carbon atoms,
• A represents a member selected from the group consisting of a polymethylene group having from 4-5 carbon atoms, and a polymethylene group having a heteroatomic group and forming a 5-6 membered ring together with a nitrogen atom;
• R R R and R each represent a member selected from the group

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• General Physics & Mathematics (AREA)
• Plural Heterocyclic Compounds (AREA)
• Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
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• 1968
  • 1968-07-08 FR FR1573520D patent/FR1573520A/fr not_active Expired
  • 1968-07-08 US US743007A patent/US3622339A/en not_active Expired - Lifetime
  • 1968-07-08 GB GB1227015D patent/GB1227015A/en not_active Expired
  • 1968-07-08 BE BE717802D patent/BE717802A/xx unknown
  • 1968-07-08 DE DE1772815A patent/DE1772815C3/de not_active Expired

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